CN100423840C - Preparation method of anatase rutile titania photocatalyst - Google Patents

Preparation method of anatase rutile titania photocatalyst Download PDF

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CN100423840C
CN100423840C CNB2006100027989A CN200610002798A CN100423840C CN 100423840 C CN100423840 C CN 100423840C CN B2006100027989 A CNB2006100027989 A CN B2006100027989A CN 200610002798 A CN200610002798 A CN 200610002798A CN 100423840 C CN100423840 C CN 100423840C
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anatase
titanium dioxide
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CN101007289A (en
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詹志洁
张忠杰
骆广生
黄丹
刁莹
李迪川
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Feng Chia University
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The invention involves preparation method of anatase type TiO2 photo-catalytic powder making use principle of liquid phase precipitation method, it mainly includes: providing solution containing titanium, making the solution containing titanium and an acidic or alkaline solution react and purify at room temperature, said alkaline solution can be caustic soda, ammonium hydroxide and potassium hydrate, said acidic solution can be nitric acid, sulfuric acid, phosphoric acid, hydrochloric acid and boric acid. It is analyzed and displayed that by apparatus that, the titanium oxide powder prepared in the invention is anatase type TiO2, and according the photocatalysis experiments and antibiotic testing experiment results, the titanium oxide powder prepared in the invention has good photocatalysis and antibiotic performance.

Description

The preparation method of anatase rutile titania photocatalyst
Technical field
The present invention relates to a kind of anatase titanium dioxide (TiO that utilizes the liquid-phase precipitation method preparation to can be applicable to photocatalyst 2) method of powder, refer in particular to the method for the gentle and simple synthesizing anatase type titanium dioxide powder of a kind of reaction condition.
Background technology
Titanium dioxide (TiO 2) owing to its structure and qualitative outstanding advantage become the most attractive semiconductor photocatalyst, having broad application prospects aspect light-catalyzed reaction and the environmental protection, and the crystal formation of titanium dioxide has significant effects to its catalytic activity.In three kinds of crystal formations of titanium dioxide, the brookite type instability is a kind of metastable phase; Detitanium-ore-type (anatase) because of its surface to oxygen (O 2) adsorption capacity stronger, have advantages of high catalytic activity; Its surperficial electronics of rutile-type (rutile) titanium dioxide is very fast with the speed that combines again in electric hole, and therefore the catalytic capability that shows is relatively poor.At present, the method for preparing titanium dioxide mainly contains sol-gal process, microemulsion method, the precipitation method, hydro-thermal method, chemical vapour deposition technique etc.In TW349981, utilize titanium tetrachloride (TiCl 4) be predecessor,,, after adding the hydrogen peroxide reaction below 15 ℃, cultivate 7-10 day down in normal temperature again to pH=2-6 with ammonia water titration, can make armorphous titanium peroxide sol, but must be through just having photocatalytic activity after high temperature (250 ℃-940 ℃) calcining.In TW363941, utilize titanyl sulfate (TiOSO 4) be predecessor, behind 80 ℃ of-100 ℃ of following hydrolysis, under 90 ℃ of-110 ℃ of temperature, carried out precipitation reaction 200-400 minute again, can make armorphous titanium dioxide powder, through just obtaining the anatase titanium dioxide powder after 460 ℃ of-1020 ℃ of multistage high-temperature calcinations.In TW393342, utilize titanyl sulfate (TiOSO 4) be predecessor, can make the photocatalyst of titanium dioxide powder after adding water decomposition.In TW541285, utilize titanium salt or compound to be predecessor, after 0.5-8 hour, can make the anatase titanium dioxide powder with the hydro-thermal method reaction under 100 ℃-350 ℃.In the CN1491897 patent, utilize titanium tetrachloride (TiCl 4), titanium sulfate (Ti (SO 4) 2), titanyl sulfate (TiOSO 4) be predecessor, after the adding nucleus promoter, form hydrated titanium dioxides 20 ℃-120 ℃ following hydrolysis, after 40 ℃ of-120 ℃ of dryings, can make the anatase rutile titania photocatalyst powder again.In the US4923682 patent, utilize titanium oxychloride (TiOCl 2) be predecessor, add nucleus promoter after, under the saturated boiling temperature environment of solution hydrolysis 2-5 hour, after 0.5-2 hour, can make the anatase titanium dioxide powder with 500 ℃-750 ℃ calcinings again.In the US5024827 patent, utilize titanium oxychloride (TiOCl 2) be predecessor, after the adding nucleus promoter, descended hydrolysis 10-30 minute in saturated boiling temperature (about 200 ℃) with hydro-thermal method, again with after 500 ℃ of-950 ℃ of calcinings, can make the anatase titanium dioxide powder.In the US5147629 patent, utilize titanium tetrachloride (TiCl 4) be predecessor, 50 ℃ add nucleus promoter under the saturated boiling point environment to solution after, can make the anatase titanium dioxide powder.In the US5330953 patent, with titanyl sulfate (TiOSO 4) be predecessor, add the rutile crystallization inhibitor simultaneously, behind 20 ℃ of-50 ℃ of following hydrolysis, with 500 ℃ of-800 ℃ of calcinings, can make the anatase titanium dioxide powder again.In the US5630995 patent, with titanium sulfate (Ti (SO 4) 2), titanyl sulfate (TiOSO 4) be predecessor, after 80 ℃ of-110 ℃ of following hydrolysis 3-4 hours, with after 460 ℃ of-1010 ℃ of multistage high-temperature calcinations, can make the anatase titanium dioxide powder again.In the US6001326 patent, utilize titanium tetrachloride (TiCl 4) be predecessor, in 15 ℃-155 ℃, under the 4bar hyperbaric environment hydrolysis 2-60 hour, can make the anatase titanium dioxide powder.In the US6440383 patent, with titanium tetrachloride (TiCl 4) be predecessor, under 120 ℃-250 ℃,, with after 450 ℃ of-1100 ℃ of high-temperature calcinations, can make the anatase titanium dioxide powder again with the reaction that is hydrolyzed of spray-drying mode.In the US6517804 patent, utilize titanium tetrachloride (TiCl 4) be predecessor, at 15 ℃ of-70 ℃ of following hydrolysis 2-20 hours, and then clean after filtration and drying after, after 10-40 hour, can make the anatase rutile titania photocatalyst powder with 300 ℃ of calcinings.In the US6576589 patent, with alcoxyl alcohol titanium (Ti (OR) 4), titanyl sulfate (TiOSO 4), titanium tetrachloride (TiCl 4) be predecessor, at 60 ℃ of-100 ℃ of following hydrolysis 2-10 hours, can make anatase titanium dioxide powder and film.In the US6740312 patent, with titanium oxychloride (TiOCl 2) be predecessor, under citric acid or other organic acid soln with 50 ℃-110 ℃ hydrolysis 2-3 hour, can make the anatase titanium dioxide powder.People such as Nagayama (Nagayama, H.; Honda, H.; Kawahara, H., J.Electrochem.Soc., 135 (1988) 2013) in 1988 a kind of new method of utilizing supersaturated solution to prepare metal-oxide film--liquid phase deposition (Liquid Phase Deposition) has been proposed, can under room temperature, make the film of metal oxide.People (Deki, S. such as Deki in 1996; Aoi, Y.; Hiroi, O.; Kajinami, A., Chem.Lett., 6 (1996) 433) at first use liquid phase deposition with hexafluoro titanium ammonium ((NH 4) 2TiF 6) and boric acid be raw material, can be directly under room temperature condition on glass baseplate deposition obtain TiO 2Film, the titanium deoxid film that this method makes under the room temperature are amorphous state, need just can obtain anatase titanium dioxide through 400 ℃ of high-temperature calcination heat treatments.In TW374243 and TW389942, equally also utilize hexafluoro metatitanic acid (H with liquid phase deposition 2TiF 6) be predecessor, add acidic aqueous solution, in 15 ℃-70 ℃ carry out deposition reaction after, can on semiconductor substrate, deposit the acquisition titanium deoxid film.People such as Zhao Wenkuan (Zhao Wenkuan, Fang Youling, Acta PhySico-Chimica Sinica, 18 (4) (2002) 368) utilize liquid phase deposition with hexafluoro titanium ammonium ((NH 4) 2TiF 6) and boric acid be raw material, in deposit fluid, add simultaneously the anatase titanium dioxide nanocrystal as the crystallization derivant, can be under 35 ℃-65 ℃ temperature conditions, directly deposition obtains Detitanium-ore-type TiO on glass baseplate 2Film, but sedimentation time reached more than 20 hours.
Comprehensively the above prepares anatase titanium dioxide (TiO at present 2) method of powder or film, must or add nucleus promoter or under the synthesis condition of HTHP and tediously long measures such as sedimentation time through the high-temperature calcination heat treatment more than 300 ℃, just can make the titanium dioxide crystallization obtain anatase titanium dioxide, not only operating procedure complexity, energy resource consumption height, and high-temperature calcination also can cause the reunion of titanium dioxide granule, reduce specific area, be unfavorable for the carrying out of light-catalyzed reaction, still remain further to be solved.
Summary of the invention
Main purpose of the present invention is to provide a kind of anatase titanium dioxide (TiO 2) preparation method of photocatalyst powder, can under the reaction condition of gentleness, prepare the anatase titanium dioxide (TiO that provides good light catalytic performance and antibacterial efficacy 2) powder, do not need again through high-temperature calcination heat treatment or long deposition.
For achieving the above object, the invention provides a kind of anatase titanium dioxide (TiO 2) preparation method of photocatalyst powder, it comprises:
Titaniferous solution is provided;
Described titaniferous solution and a kind of alkaline solution or acid solution are evenly mixed;
In reacting below 100 ℃;
Obtain anatase titanium dioxide product powder after the purified drying.
Preferably, described alkaline solution is optional self-contained by NaOH (NaOH), ammonium hydroxide (NH 4OH) and the alkaline solution group that formed of potassium hydroxide (KOH), and reaction temperature is between 50 ℃-100 ℃, and more preferably, reaction temperature is between 70 ℃-100 ℃.
Preferably, described acid solution is optional self-contained by boric acid (H 3BO 3), nitric acid (HNO 3), hydrochloric acid (HCl), sulfuric acid (H 2SO 4) and phosphoric acid (H 3PO 4) the acid solution group that formed, and reaction temperature is between 50 ℃-100 ℃, and more preferably, reaction temperature is between 50 ℃-80 ℃.
Preferably, the concentration of described alkaline solution is at least about 0.1M, and more preferably, the concentration of this alkaline solution is at least about 0.2M.
Preferably, the concentration of described acid solution is at least about 0.1M, and more preferably, the concentration of this acid solution is at least about 0.6M.
Preferably, the chemical formula of described titaniferous solution is (M) 2TiF 6, and M comprises K, Na, H, NH for being selected from 4A kind of in the cluster ion of being formed.
Preferably, the titanium ion concentration of described titaniferous solution is at least about 0.1M, and more preferably, the titanium ion concentration of this titaniferous solution is at least about 0.4M.
Preferably, described titaniferous (M) 2TiF 6The volume ratio of solution and alkaline solution or acid solution is about 1: 1.
Preferably, described reactive mode can be batch formula operation or continous way operant response.
Preferably, described purifying drying comprise product is separated after further with behind deionized water and the absolute ethanol washing, carry out 80 to 120 ℃ of vacuum drying.
Preparation method of the present invention can make Detitanium-ore-type TiO under the reaction condition of gentleness 2The photocatalyst powder need not pass through the step complexity, power consumption has the high-temperature calcination heat treatment of high risk again, does not also need waste to wait as long for deposition reaction.So anatase titanium dioxide (TiO of the present invention 2) preparation method of photocatalyst powder, not only the temperature of technology is low, energy savings, simple to operate, with low cost, and prepared anatase titanium dioxide (TiO 2) powder is with good photocatalysis performance, and good antibacterial efficacy, has the value on commercial the application.
Description of drawings
Figure 1A and Figure 1B are the titanium dioxide powder XRD spectra of the present invention's preparation.
Fig. 2 A and Fig. 2 B are the titanium dioxide powder photocatalysis usefulness figure of the present invention's preparation.
Fig. 3 A and Fig. 3 B are the titanium dioxide powder antibacterial experiment contrast figure of the present invention's preparation.
The specific embodiment
The invention provides a kind of anatase titanium dioxide (TiO 2) preparation method of photocatalyst powder, can and need not add under the condition of crystal seed at temperate condition by method provided by the present invention, utilize the principle of liquid-phase precipitation to obtain anatase titanium dioxide (TiO 2) powder, it mainly is according to liquid-phase precipitation method, under specific reaction conditions, at first utilizes a titaniferous materials solution to mix with specific alkaline solution or acid solution and stirs, and the titanium dioxide reaction is formed.The chemical formula of described titaniferous solution is (M) 2TiF 6, and M is K, Na, H or NH 4, but be not limited thereto.Described this alkaline solution can be solution such as NaOH, ammonium hydroxide, potassium hydroxide, but is not limited to these kinds; Described acid solution can be solution such as nitric acid, sulfuric acid, phosphoric acid, hydrochloric acid, boric acid, but is not limited to these kinds.With reacted product centrifugation and cleaning back vacuum drying under 80 to 120 ℃ of conditions, can make anatase titanium dioxide (TiO 2) the photocatalyst powder.
Utilize X-ray diffractometer (XRD), full-automatic physical and chemical adsorption analyzer (BET) isothermal absorption mode to survey modes such as specific area, to prepared Detitanium-ore-type TiO 2Powder carries out phenetic analysis; Test for the light-catalyzed reaction object carries out photocatalysis with the methyl orange aqueous solution again, assess its photocatalysis performance; And carry out antibacterial test with Escherichia coli, assess its antibacterial efficacy.Experimental result shows the prepared TiO of the present invention 2Powder all is single Detitanium-ore-type, its crystallite dimension ratio commercialization
Figure C20061000279800081
TiO 2P25 (German Degussa group produce) is little, and specific area is bigger, and has good photocatalysis performance, and antibacterial test also shows to have good antibacterial efficacy.
Embodiment one: anatase titanium dioxide (TiO 2) preparation of powder
The preparation method of anatase titanium dioxide powder of the present invention mainly includes following steps:
The titaniferous solution of preparation debita spissitudo is preferably (NH 4) 2TiF 6The aqueous solution, (NH of concentration 0.4M preferably in the present embodiment 4) 2TiF 6The aqueous solution makes this (NH 4) 2TiF 6The aqueous solution and one can with (NH 4) 2TiF 6The solution that the aqueous solution reacts mixes.In the present invention, because the Ti ion is transition elements, its electron configuration can react with acid or aqueous slkali, therefore described can with (NH 4) 2TiF 6The solution that the aqueous solution reacts can be acid solution or alkaline solution, and preferred acid solution can be boric acid (H 3BO 3), preferred alkaline solution can be NaOH, NH 4OH or KOH.In specific embodiments of the invention, preferably the NaOH aqueous solution or the NH of 0.2M 4The OH aqueous solution.
Two solution are mixed by 1: 1 volume ratio, be lower than under 100 ℃ the condition (in the present invention, preferred and acid solution reaction temperature is 50 ℃ to 100 ℃, with alkaline solution reaction temperature be 80 ℃ to 100 ℃), short time reacts, and finishes reaction being less than in 4 hours.
Fully wash with deionized water and absolute ethyl alcohol after will reacting back products therefrom centrifugation, under 100 ℃ of conditions, carry out vacuum drying then, can obtain Detitanium-ore-type TiO 2The powder of photocatalyst.
Embodiment two: the anatase titanium dioxide (TiO of system that different condition obtains 2) phenetic analysis of powder
Shown in Figure 1A and Figure 1B, the prepared anatase titanium dioxide powder of the present invention can see at 25.5 °, 38 °, 47 °, 54 ° and 62 ° and locate tangible X-ray diffraction maximum with the XRD figure analysis of spectrum, with commercial on the market
Figure C20061000279800082
TiO 2P25 is inequality, is (NH no matter illustrate 4) 2TiF 6With H 3BO 3Under 50 ℃ of-100 ℃ of reaction conditions, react, or (NH 4) 2TiF 6With NaOH, NH 4Three kinds of different alkaline solutions such as OH or KOH react resultant TiO under 80 ℃ of-100 ℃ of reaction conditions 2The crystal formation of powder all is single anatase phase.Its X-ray characteristic diffraction peak broad, the expression The grain size is less.
As shown in the following Table I, with BET specific area, pore volume and the pore-size distribution of full-automatic physical and chemical adsorption analysis-e/or determining sample, the prepared powder body material specific area of its presentation of results is all than commercialization
Figure C20061000279800091
TiO 2P25 is big.
Table one
Figure C20061000279800092
Embodiment three: the photocatalysis performance assessment
Carry out the photocatalysis experiment according to following listed step:
The 10ppm methyl orange aqueous solution 100ml of preparation pH=3 inserts in the 125ml conical flask;
Weigh 0.1 the gram titanium dioxide powder and insert in the aforesaid conical flask;
Place the stirring of airtight darkroom after 12 hours the solution of being prepared, then, carried out light-catalyzed reaction 4 hours with the UV-irradiation of wavelength 365nm;
After reaction finishes, the catalyst titanium dioxide powder is reclaimed in centrifugal mode, and dry.
The goal response that is degraded to methyl orange aqueous solution, detect the photocatalysis performance of titanium dioxide powder, the high more then photocatalysis performance of methyl orange aqueous solution degradation rate in the short more time is good more, in the solution concentration of methyl orange with the variation relation in reaction time shown in Fig. 2 A and Fig. 2 B, the result shows that the prepared titanium dioxide powder of the present invention has good photocatalytic activity, utilizes (NH 4) 2TiF 6With H 3BO 3The degradation rate of prepared 4 hours methyl orange of product reaction can reach about 50% to 65%.Under identical photocatalytic reaction conditions, (NH 4) 2TiF 6With NaOH, NH 4Three kinds of prepared products of Different Alkali such as OH or KOH, 4 hours degradation rate of methyl orange all levels off to about 100%.(NH 4) 2TiF 6With KOH its photocatalysis usefulness of product and commercialization 80 ℃ of reactions
Figure C20061000279800101
TiO 2P25 is very approaching; And (NH 4) 2TiF 6With NaOH or NH 4OH all is better than commercialization in its photocatalysis usefulness of product of 80 ℃ of reactions
Figure C20061000279800102
TiO 2P25 is a lot, learns the TiO that the present invention is prepared thus 2Powder has good photocatalysis performance.
Embodiment four: the antibacterial efficacy assessment
Utilize the prepared anatase titanium dioxide powder of the present invention to come to carry out the antibacterial test experiment at Escherichia coli (the BCRC number:BCRC of Foodstuff Industrial and Development Inst. 51731 Escherichia coliDH5 α), this experiment is divided into blank group (irradiation but without the sample of anatase titanium dioxide powder handling) and experimental group (irradiation and through the sample of anatase titanium dioxide powder handling), add that at 35 ℃ UV-A (wavelength 365nm) light source carried out constant temperature culture 24 hours under shining, test mode can reach the antibacterial efficacy of the prepared anatase titanium dioxide powder of assessment thus.Can find out clearly that from Fig. 3 A and Fig. 3 B blank group (Fig. 3 A) significantly has the situation of bacterial multiplication to take place, experimental group (Fig. 3 B) does not significantly almost completely have bacterium to occur.Can learn that thus the prepared anatase titanium dioxide powder of the present invention also possesses simultaneously good antibacterial efficacy is arranged.
The difference correction that can do according to the present invention and variation all obviously can not depart from scope of the present invention and spirit for those of ordinary skill in the art.Though the present invention has narrated specific preferred specific embodiment, it must be appreciated that the present invention should be limited on these certain specific embodiments undeservedly.In fact, implementing of the present invention having stated aspect the pattern, apparent and easy to know different the correction also is included in protection scope of the present invention for those of ordinary skill in the art.

Claims (8)

1. the preparation method of an anatase rutile titania photocatalyst powder, it comprises:
Titaniferous solution is provided, and the chemical formula of described titaniferous solution is (M) 2TiF 6
Titaniferous solution is evenly mixed with a kind of alkaline solution;
Reacting below 100 ℃;
Obtain anatase titanium dioxide product powder after the purified drying.
2. the preparation method of anatase rutile titania photocatalyst powder as claimed in claim 1 is characterized in that, M comprises K, Na, H, NH for being selected from 4A kind of in the cluster ion of being formed.
3. the preparation method of anatase rutile titania photocatalyst powder as claimed in claim 1 or 2 is characterized in that, the titanium ion concentration of titaniferous solution is at least 0.1M.
4. the preparation method of anatase rutile titania photocatalyst powder as claimed in claim 3 is characterized in that, titaniferous solution is 1: 1 with the reaction volume ratio of alkaline solution.
5. the preparation method of anatase rutile titania photocatalyst powder as claimed in claim 4 is characterized in that, operation is batch formula operation or continous way operant response.
6. the preparation method of anatase rutile titania photocatalyst powder as claimed in claim 5 is characterized in that, the purifying drying comprise product is separated after further with deionized water and absolute ethanol washing, carry out vacuum drying again.
7. the preparation method of anatase rutile titania photocatalyst powder as claimed in claim 3 is characterized in that, alkaline solution concentration is at least 0.1M.
8. the preparation method of anatase rutile titania photocatalyst powder as claimed in claim 3 is characterized in that, the reaction temperature of titaniferous solution and alkaline solution is 50 to 100 ℃.
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CN103801277A (en) * 2012-11-14 2014-05-21 上海纳米技术及应用国家工程研究中心有限公司 Titanium dioxide nanoribbon photocatalyst and preparation and applications thereof
CN106243680B (en) * 2016-08-01 2020-11-17 江苏卧尔康家居用品有限公司 Preparation method of nano titanium dioxide reinforced polyurethane material
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Publication number Priority date Publication date Assignee Title
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TW374243B (en) * 1998-05-20 1999-11-11 Winbond Electronics Corp Method for manufacturing a liquid phase titanium dioxide film
CN1348430A (en) * 1999-04-23 2002-05-08 内诺株式会社 Method for manufacturing photocatalytic titanium dioxide powder
US6387446B1 (en) * 1998-10-01 2002-05-14 Fraun-Hofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. Method for depositing titanium oxide layers using soluble powders
US6576589B1 (en) * 1999-09-20 2003-06-10 Lg Electronics Inc. Method for making anatase type titanium dioxide photocatalyst
CN1491897A (en) * 2002-10-23 2004-04-28 中国科学院化学研究所 Low temperature preparing process for anatase phase nano crystal titanium dioxide of light catalystic activity

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1135459A (en) * 1995-01-20 1996-11-13 泰奥塞集团服务有限公司 Detitanium-ore-type preparation of titanium dioxide
TW374243B (en) * 1998-05-20 1999-11-11 Winbond Electronics Corp Method for manufacturing a liquid phase titanium dioxide film
US6387446B1 (en) * 1998-10-01 2002-05-14 Fraun-Hofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. Method for depositing titanium oxide layers using soluble powders
CN1348430A (en) * 1999-04-23 2002-05-08 内诺株式会社 Method for manufacturing photocatalytic titanium dioxide powder
US6576589B1 (en) * 1999-09-20 2003-06-10 Lg Electronics Inc. Method for making anatase type titanium dioxide photocatalyst
CN1491897A (en) * 2002-10-23 2004-04-28 中国科学院化学研究所 Low temperature preparing process for anatase phase nano crystal titanium dioxide of light catalystic activity

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